KR20160109645A - Cleanig composition for photoresist - Google Patents

Abstract

The present invention relates to a washing liquid composition for removing a photoresist and, more specifically, to a washing liquid composition for removing a photoresist, and a producing method for a semiconductor substrate using the same. The washing liquid composition for removing a photoresist has excellent removing ability with respect to a modified photoresist modified by plasma gas or ions as well as a general photoresist by comprising a fluorine-based compound, alkane sulfonic acid having 1 to 4 carbon numbers, an azole-based compound, and an organic solvent, and can minimize damages of a power portion silicon oxide film and a metal film.

Description

[0002] CLEANIG COMPOSITION FOR PHOTORESIST [0003]

The present invention relates to a cleaning liquid composition for removing a photoresist, and more particularly, to a cleaning liquid composition capable of effectively removing a photoresist without damaging a lower silicon oxide film and a metal film.

Photoresist is a chemical film that can form a fine pattern pre-drawn on a photomask on a desired substrate by using photochemical reaction by light. It is used as a polymer material applied to exposure technology together with a photomask. Is directly recognized as a major factor in determining the ultimate resolution limit. In order to put the increasing degree of circuit integration into a semiconductor of limited size every year according to the so-called Moore's law (the theory that semiconductor density doubles every two years), the designed circuit must be patterned much smaller Increasing semiconductor density is inevitably demanding the development of new photoresists.

A photolithography process for forming fine wiring on a substrate using such a photoresist is generally used in order to manufacture a high resolution flat panel display (semiconductor device or the like) Is coated with a photoresist, exposed to light of a certain wavelength, and subjected to dry etching or wet etching.

In the fine patterning technique using a photoresist, a development that has been emphasized with respect to a new photoresist is a resist stripper (or a photoresist remover). The photoresist must be removed by a solvent called Stripper (or Photoresist Remover) after the etching process. This is because unnecessary photoresist layer after the etching process and etching of the metal residue or deteriorated photo This is because the resist residues cause problems such as a decrease in the yield of semiconductor production.

Typical examples of the dry etching method include plasma etching and ion implantation etching. In the plasma etching, a gas-solid reaction between a plasma gas and a material layer such as a conductive layer is used to perform an etching process The ions and radicals of the plasma etching gas chemically react with the photoresist to harden and denature the photoresist film, which makes it difficult to remove the photoresist film. The ion implantation process is a process of diffusing phosphorus, arsenic, boron, or the like phosphorus in order to impart conductivity to a specific region of a substrate in a manufacturing process of a semiconductor / LED / LCD device. So that the removal becomes difficult.

Thus, it is possible to obtain a remarkable level of removal power against etching residues and an excellent peeling force against deteriorated photoresist residues, specifically, a removal power against etch residues generated after the dry etching process, The peeling property is required.

Korean Patent Publication No. 2011-0130563 discloses a photoresist stripper composition.

Korea Patent Publication No. 2011-0130563

It is an object of the present invention to provide a cleaning liquid composition for removing photoresist which has an excellent removal power against a modified photoresist.

It is another object of the present invention to provide a cleaning liquid composition for removing photoresist which can minimize damage to a lower metal film and a silicon oxide film.

It is another object of the present invention to provide a method of manufacturing a semiconductor substrate using the cleaning composition of the present invention.

1. A cleaning liquid composition for removing photoresist, comprising at least one compound selected from compounds represented by Chemical Formulas 1 and 2, an alkanesulfonic acid having 1 to 4 carbon atoms, an azole-based compound, and an organic solvent:

[Chemical Formula 1]

(R ¹ ) ₄ N ⁺ F ^-

(2)

(R ² ) ₄ N ⁺ HF ^{2 -}

(Wherein R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms).

2. The cleaning liquid composition for removing photoresist according to 1 above, wherein the cleaning liquid is non-aqueous.

3. The composition of claim 1, wherein the compound of Formula 1 is selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, tetrahexylammonium fluoride , Tetraheptyl ammonium fluoride, and tetraoctyl ammonium fluoride.

4. The composition of claim 1, wherein the compound of Formula 2 is selected from the group consisting of tetramethylammonium bifluoride, tetraethylammonium bifluoride, tetrapropylammonium bifluoride, tetrabutylammonium bifluoride, tetrapentylammonium bifluoride, Wherein the cleaning liquid composition comprises at least one selected from the group consisting of tetrahexylammonium bifluoride, tetraheptylammonium bifluoride, and tetraoctylammonium bifluoride.

5. The cleaning liquid composition for removing photoresist according to item 1, wherein the alkanesulfonic acid having 1 to 4 carbon atoms includes at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid.

6. The method of claim 1, wherein the azole-based compound is selected from the group consisting of 1,2-dimethylimidazole, 1-isopropylimidazole, 1-propyl-2-methylimidazole, benzylimidazole, , At least one selected from the group consisting of 2,3-triazole, benzotriazole, 5-amino-1-tetrazole and 5-benzyl-1-tetrazole.

7. The cleaning liquid composition for removing photoresist according to item 1 above, wherein the organic solvent is a polar protic solvent.

8. The composition according to 1 above, which comprises 1 to 20% by weight of at least one compound selected from the group consisting of compounds represented by the general formulas (1) and (2), 1 to 20% by weight of an alkanesulfonic acid having 1 to 4 carbon atoms, % By weight of an organic solvent and 60 to 97% by weight of an organic solvent.

9. The cleaning liquid composition for removing photoresist according to item 1 above, wherein the photoresist is modified during a dry etching process.

10. The cleaning liquid composition for removing photoresist as described in 1 above, wherein the photoresist has a metal film formed thereunder.

11. The cleaning liquid composition for removing photoresist according to item 10, wherein the metal film is an aluminum-based metal film.

12. The cleaning liquid composition for removing photoresist as described in 1 above, wherein the photoresist has a silicon oxide film formed on a lower portion thereof.

13. A method comprising: i) forming a metal film on a substrate;

II) forming a silicon oxide film on the metal film;

III) forming a photoresist pattern on the silicon oxide film by a photolithography process;

(IV) dry etching the silicon oxide film on which the photoresist pattern is formed; And

V) cleaning said etched film with a cleaning composition according to any one of claims 1 to 12;

And forming a semiconductor layer on the semiconductor substrate.

The cleaning liquid composition of the present invention has an excellent removing power not only for a general photoresist but also for a denatured photoresist denatured by a plasma gas or an ion.

The cleaning composition of the present invention can minimize damage to the lower silicon oxide film and the underlying metal film during cleaning.

Further, the cleaning liquid composition of the present invention is excellent in stability over time.

More particularly, the present invention relates to a cleaning liquid composition for removing a photoresist, which comprises a fluorine-based compound, an alkane sulfonic acid having 1 to 4 carbon atoms, an azole-based compound and an organic solvent, The present invention relates to a cleaning liquid composition for removing a photoresist and a method of manufacturing a semiconductor substrate using the same, which is capable of minimizing damage to a lower silicon oxide film and a metal film while having an excellent removal power against a modified photoresist.

As used herein, the term "denatured photoresist" refers to a photoresist that is cured and denatured by a chemical reaction with ions and radicals of the plasma etch gas during plasma etching (dry etching), a photoresist that is denatured Quot; photoresist "

The photoresist is formed on the top of the silicon oxide film and the metal film. In the case of a conventional photoresist cleaning solution composition, the removal power of the modified photoresist deteriorates, or only the resist removal force is excessively increased to damage the lower silicon oxide film and the metal film However, the cleaning liquid composition for removing the photoresist of the present invention has an excellent removing power against the modified photoresist, and at the same time, the damage to the lower silicon oxide film and the metal film can be minimized.

Hereinafter, the present invention will be described in detail.

< Photoresist  Cleaning liquid composition for removing>

The cleaning liquid composition for removing photoresist of the present invention comprises at least one compound represented by the following general formula (1) or (2), an alkanesulfonic acid having 1 to 4 carbon atoms, an azole-based compound, and an organic solvent.

It is preferable that the cleaning liquid composition for removing photoresist according to the present invention is nonaqueous. In the present invention, &quot; nonaqueous system &quot; means that substantially no water is used as a solvent. Of the total amount of water, and the amount of water contained in the water is not excluded.

The nonaqueous cleaning liquid composition for removing photoresist of the present invention does not use water as a solvent and does not excessively increase the activity of hydrogen fluoride (HF) in the composition, It is possible to effectively remove the photoresist without damaging it.

(1) or Alkylammonium fluoride

The cleaning liquid composition of the present invention comprises at least one compound selected from among compounds represented by the following general formula (1) or (2).

[Chemical Formula 1]

(R ¹ ) ₄ N ⁺ F ^-

(2)

(R ² ) ₄ N ⁺ HF ^{2 -}

(Wherein R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms).

The compound represented by the above formula (1) or (2) is a component for removing the photoresist, and can generate hydrogen fluoride (HF) through reaction with the alkane sulfonic acid of the present invention described below to effectively remove the denatured photoresist.

On the other hand, when inorganic ammonium fluoride is used, the organic solvent alone can not dissolve and water must be used as a solvent. In this case, the activity of hydrogen fluoride (HF) is excessively increased by the water, There was a problem causing angles.

However, the present invention makes it possible to effectively remove the photoresist without damaging the underlying metal film and the silicon oxide film by using the alkylammonium fluoride represented by the general formula (1) or (2).

The type of the compound represented by Formula 1 is not particularly limited, and examples thereof include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, tetra Hexylammonium fluoride, tetraheptylammonium fluoride, tetraoctylammonium fluoride, etc. These may be used alone or in admixture of two or more.

The kind of the compound represented by the formula (2) is not particularly limited, and examples thereof include tetramethylammonium bifluoride, tetraethylammonium bifluoride, tetrapropylammonium bifluoride, tetrabutylammonium bifluoride, tetrapentylammonium Tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide, tetrahexylammonium bromide and tetraoctylammonium bromide.

The content of the compound represented by the above formula (1) or (2) is not particularly limited, but may be, for example, 1 to 20% by weight, and preferably 2 to 10% by weight based on the total weight of the cleaning liquid composition. If the above range is satisfied, the denatured photoresist can be removed at an appropriate rate, and defects for the lower wiring and damages to the lower silicon oxide film can be suppressed. On the other hand, if it is more than 20% by weight, the solubility of the composition is reduced, and the fluoride compound may precipitate and cause defects of the metal film.

Carbon number  1 to 4 Alkanesulfonic acid

The alkanesulfonic acid having 1 to 4 carbon atoms used in the cleaning liquid composition of the present invention is a component that generates hydrogen fluoride (HF) through reaction with the compound of the above formula (1) or (2) to remove the denatured photoresist.

Since the cleaning liquid composition of the present invention generates hydrogen fluoride (HF) in the composition, it does not need to separately add hydrogen fluoride (HF) and is safer in use.

In addition, it is considered that the sulfone group of the alkanesulfonic acid can form a coating of a chelate compound on the surface of the metal film, thereby remarkably improving the corrosion preventing effect.

Examples of the alkanesulfonic acid having 1 to 4 carbon atoms include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, etc. These may be used alone or in admixture of two or more. Methanesulfonic acid is preferably used.

The content of the alkanesulfonic acid having 1 to 4 carbon atoms is not particularly limited, but may be, for example, 1 to 20% by weight, and preferably 1 to 10% by weight based on the total weight of the cleaning liquid composition. When the above range is satisfied, the denatured photoresist can be removed at an appropriate rate, and at the same time, defects on the lower wiring can be suppressed. On the other hand, if it exceeds 20% by weight, the stability of the cleaning liquid composition may deteriorate to cause a color change, lowering the removal rate of the photoresist, and causing defects of the metal film.

Azole series  compound

The azole compound used in the cleaning liquid composition of the present invention is a component for preventing damage to the lower silicon oxide film and the metal film during cleaning and can effectively prevent damage to the lower silicon oxide film and the metal film by increasing the pH of the composition.

On the other hand, the conventional additives for preventing the damage of the silicon oxide film cause a reaction with the alkanesulfonic acid to lower the reaction with the alkylammonium fluoride with the alkanesulfonic acid. On the other hand, the azole compound according to the present invention does not cause a side reaction with the alkane sulfonic acid upon washing, and can more effectively protect the lower film.

The azole compound is not particularly limited, and examples thereof include 1,2-dimethylimidazole, 1-isopropylimidazole, 1-propyl-2-methylimidazole, benzylimidazole, 4 Amino-1,2,3-triazole, benzotriazole, 5-amino-1-tetrazole and 5-benzyl-1-tetrazole. These may be used alone or in combination have.

The content of the azole compound is not particularly limited and may be, for example, 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total weight of the cleaning liquid composition. When the above range is satisfied, the protection effect of the lower silicon oxide film and the metal film can be maximized. On the other hand, if it exceeds 5% by weight, the removal rate of the photoresist may be lowered.

Organic solvent

The organic solvent used in the cleaning liquid composition of the present invention is capable of dissolving the above components, and the kind thereof is not particularly limited.

Specific examples thereof include glycols such as ethylene glycol, propylene glycol, butylene glycol and the like;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkyl acetates such as methyl acetate, ethyl acetate, butyl acetate and propyl acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, diacetone alcohol, and tetrapuryl alcohol;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone, and the like, and polar aprotic solvents are preferred.

The content of the organic solvent is not particularly limited, but may be, for example, from 60 to 97% by weight, and preferably from 80 to 90% by weight, based on the total weight of the cleaning liquid composition. When the above range is satisfied, the optimum etching rate and solubility can be shown.

The cleaning liquid composition of the present invention may further contain conventional additives, if necessary, in addition to the above-mentioned components. Examples of the additive include, but are not limited to, an etch control agent, a metal ion sequestrant, a corrosion inhibitor, a surfactant, and a pH adjuster.

The photoresist to be cleaned with the cleaning liquid composition according to the present invention may be not only a general photoresist but also a modified photoresist modified by a plasma gas or ion (dry etching), and a metal film and / or a silicon oxide film is formed under the photoresist Lt; / RTI &gt;

<Method of Manufacturing Semiconductor Substrate>

The present invention relates to a method of manufacturing a semiconductor substrate using the cleaning composition of the present invention.

A method of manufacturing a semiconductor substrate according to an embodiment of the present invention includes the steps of: I) forming a metal film on a substrate; II) forming a silicon oxide film on the metal film; III) forming a photoresist pattern on the silicon oxide film by a photolithography process; (IV) dry etching the silicon oxide film on which the photoresist pattern is formed; And V) cleaning the etched film with the cleaning composition according to the present invention.

The type of the metal film is not particularly limited, but may be, for example, an aluminum-based metal film, and the aluminum-based metal film includes aluminum (Al) as a constituent component of the film and may be a multilayer film such as a single film, .

For example, the aluminum alloy film may include a single film of an alloy of aluminum or aluminum, and the aluminum alloy film may include at least one selected from the group consisting of nickel (Ni), indium (In), magnesium (Mg), manganese (Mn) (Hf), niobium (Nb), tungsten (W) and vanadium (V), silver (Ag), molybdenum (Mo), titanium (Ti), copper (Cu), palladium La), or an aluminum alloy film composed of a nitride (for example, TiAlN) or a carbide (for example, TiAlC) of the aluminum alloy.

The method of manufacturing a semiconductor substrate according to the present invention includes a cleaning step using the cleaning composition of the present invention as described above so that the modified photoresist can be effectively removed and damage to the lower silicon oxide film and the metal film can be minimized have.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  And Comparative Example

division
(weight%) Organic acid Alkylammonium
Fluoride ammonium
Fluoride additive Organic solvent Deionized water ingredient content ingredient content ingredient content ingredient content ingredient content Example 1 A-1 5 B-1 5 - - D-1 One E-1 89 - Example 2 A-1 5 B-1 5 - - D-2 One E-1 89 - Example 3 A-1 5 B-1 5 - - D-3 One E-1 89 - Example 4 A-1 5 B-2 5 - - D-1 One E-1 89 - Example 5 A-1 5 B-2 5 - - D-2 One E-1 89 - Example 6 A-1 5 B-2 5 - - D-3 One E-1 89 - Example 7 A-1 5 B-1 /
B-2 2.5 /
2.5 - - D-1 One E-1 89 - Example 8 A-1 5 B-1 /
B-2 2.5 /
2.5 - - D-2 One E-1 89 - Example 9 A-1 5 B-1 /
B-2 2.5 /
2.5 - - D-3 One E-1 89 - Example 10 A-1 5 B-1 5 - - D-1 0.1 E-1 89.9 - Example 11 A-1 5 B-1 5 - - D-1 5 E-1 85 - Example 12 A-1 5 B-1 One - - D-1 One E-1 93 - Example 13 A-1 5 B-1 10 - - D-1 One E-1 84 - Example 14 A-1 5 B-1 20 - - D-1 One E-1 74 - Example 15 A-1 5 B-1 5 - - D-1 /
D-2 0.5 /
0.5 E-1 89 - Example 16 A-1 5 B-1 5 - - D-1 /
D-3 One/
One E-1 88 - Example 17 A-1 5 B-1 5 - - D-2 /
D-3 2/
2 E-1 86 - Example 18 A-1 5 B-1 5 - - D-1 One E-2 89 - Example 19 A-1 5 B-1 5 - - D-1 One E-3 89 - Comparative Example 1 A-1 5 B-1 5 - - - - E-1 90 - Comparative Example 2 A-2 5 B-1 5 - - - - E-1 90 - Comparative Example 3 A-3 5 B-1 5 - - - - E-1 90 - Comparative Example 4 A-1 5 B-2 5 - - - - E-1 90 - Comparative Example 5 A-1 5 B-1 5 - - - - E-2 90 - Comparative Example 6 A-1 5 B-1 One - - - - E-1 94 - Comparative Example 7 A-1 5 B-1 10 - - - - E-1 85 - Comparative Example 8 A-1 5 B-1 20 - - - - E-1 75 - Comparative Example 9 A-1 5 - - C-1 One - - E-1 94 - Comparative Example 10 A-1 5 - - C-2 One - - E-1 94 - Comparative Example 11 A-1 5 - - C-1 One - - E-1 89 5 Comparative Example 12 A-1 5 B-1 5 - - - - E-1 85 5 Comparative Example 13 A-1 5 B-1 5 - - D-4 One E-1 89 - Comparative Example 14 A-1 5 B-1 5 - - D-5 One E-1 89 - Comparative Example 15 A-1 5 B-1 5 - - D-6 One E-1 89 - Comparative Example 16 A-1 5 B-1 5 - - D-6 0.1 E-1 89.9 - Comparative Example 17 A-1 5 B-1 5 - - D-6 5 E-1 85 - Comparative Example 18 A-1 5 B-1 5 - - D-6 One E-2 89 - Comparative Example 19 A-1 5 B-1 5 - - D-6 One E-2 84 5 A-1: Methanesulfonic acid (99%)
A-2: Para-toluenesulfonic acid
A-3: Oxalic acid
B-1: tetrabutylammonium fluoride
B-2: Tetramethylammonium bifluoride
C-1: Ammonium fluoride
C-2: Ammonium bifluoride
D-1: 1-Propyl-2-methylimidazole
D-2: benzotriazole
D-3: 3-Amino-1-tetrazole
D-4: Ammonium sulfate
D-5: Citric acid
D-6: Consumption tall
E-1: Tetrahydrofurfuryl alcohol
E-2: Ethylene glycol
E-3: Propylene glycol monomethyl ether acetate (polar aprotic solvent)

Test Methods

1) denaturation Photoresist  Removal, silicon Oxide film  And damage assessment of metal pads

After forming a silicon oxide film on a silicon wafer on which aluminum was deposited, a photoresist (193 nm) was applied, patterned through exposure and development, and plasma-etched patterned wafers were prepared. The substrate was sampled at a size of 2x2 cm and each of the compositions shown in Table 1 was prepared and then heated to 60 DEG C, and the substrate was immersed for 2 or 10 minutes. Then, the substrate was washed with water and examined under a scanning electron microscope (SEM, Hitachi S- (2 minutes immersion), Deoxidation of silicon oxide (5 minutes immersion) and Defect of Al pad (Immersion for 10 minutes) were measured by Ellipsometer (SE-MG-1000) The results are shown in Table 2.

&Lt; Criteria for removing denatured photoresist >

◎: 95% or more removed

○: 90% or more removed

△: Over 80% removed

Х: Less than 70% removed

<Standards for attck of silicon oxide film>

◎: etching rate of oxide film is less than 1 Å / min

O: Etching rate of the oxide film is 1 Å / min or more and less than 5 Å / min

DELTA: etching rate of the oxide film: 5 A / min or more and less than 10 A / min

Х: Etching rate of the oxide film exceeds 10 Å / min

<Evaluation criteria of Al pad attack>

◎: When Al pad is left over 95%

○: When the Al pad is left over 90%

DELTA: When the Al pad remains at 80% or more

Х: Al pad remains below 80%

2) Solubility evaluation (evaluation of stability over time)

The solubilities of the compositions of the above Examples and Comparative Examples were visually observed, and the results were also shown in Table 2.

<Evaluation Criteria for Solubility>

○: The bottom sediment does not occur and is transparent.

△: no precipitation occurs in the bottom, but suspension of solution occurs

X: Both precipitation and suspension of solution occur at the bottom

division Denaturing photoresist removal Silicon oxide film
damaged Aluminum pad damage Solubility Example 1 ◎ ◎ ◎ ○ Example 2 ◎ ◎ ◎ ○ Example 3 ◎ ◎ ◎ ○ Example 4 ◎ ◎ ◎ ○ Example 5 ◎ ◎ ◎ ○ Example 6 ◎ ◎ ○ ○ Example 7 ◎ ◎ ◎ ○ Example 8 ◎ ◎ ◎ ○ Example 9 ◎ ◎ ○ ○ Example 10 ◎ ○ ◎ ○ Example 11 ○ ◎ ○ ○ Example 12 ○ ◎ ◎ ○ Example 13 ◎ ○ ◎ ○ Example 14 ◎ ○ ○ ○ Example 15 ◎ ◎ ◎ ○ Example 16 ◎ ◎ ◎ ○ Example 17 ○ ◎ ◎ ○ Example 18 ◎ ○ ◎ ○ Example 19 ◎ ◎ ◎ ○ Comparative Example 1 ◎ △ ◎ ○ Comparative Example 2 △ △ ◎ ○ Comparative Example 3 ◎ X △ ○ Comparative Example 4 ◎ △ ◎ ○ Comparative Example 5 ◎ △ ◎ ○ Comparative Example 6 ○ △ ◎ ○ Comparative Example 7 ◎ △ ◎ ○ Comparative Example 8 ◎ △ ○ ○ Comparative Example 9 - - - X Comparative Example 10 - - - X Comparative Example 11 ◎ Х Х ○ Comparative Example 12 ◎ Х Х ○ Comparative Example 13 - - - X Comparative Example 14 ◎ X ○ ○ Comparative Example 15 ◎ △ ○ ○ Comparative Example 16 ◎ △ ○ ○ Comparative Example 17 ○ △ ○ ○ Comparative Example 18 ◎ △ ○ ○ Comparative Example 19 ◎ X X ○

Referring to Table 2, it was confirmed that the cleaning liquid compositions (Examples 1 to 19) according to the present invention effectively removed denatured photoresist and did not cause damage to the underlying aluminum film and silicon oxide film, and also had excellent stability with time.

However, in the case of Example 12 in which the azole compound was used in a slight excess, it was confirmed that the removing power of the modified photoresist was somewhat lowered.

Compared with the comparative examples in which the additives according to the present invention were not used or the comparative examples in which other additives were used instead of the azole compounds, damage of the silicon oxide film occurred, and in Comparative Examples 11, 12 and 19 including deionized water, It was confirmed that the aluminum pads were damaged due to excessive increase in the temperature.

Claims (13)

A cleaning liquid composition for removing photoresist, comprising at least one compound selected from compounds represented by Chemical Formulas 1 and 2, an alkanesulfonic acid having 1 to 4 carbon atoms, an azole compound, and an organic solvent:
[Chemical Formula 1]
(R ¹ ) ₄ N ⁺ F ^-
(2)
(R ² ) ₄ N ⁺ HF ^{2 -}
(Wherein R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms).
The cleaning liquid composition for removing photoresist according to claim 1, wherein the cleaning liquid is non-aqueous.
[4] The method according to claim 1, wherein the compound represented by Formula 1 is at least one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, tetrapentylammonium fluoride, tetrahexylammonium fluoride, At least one selected from the group consisting of heptylammonium fluoride and tetraoctylammonium fluoride.
[2] The method according to claim 1, wherein the compound represented by Formula 2 is at least one selected from the group consisting of tetramethylammonium bifluoride, tetraethylammonium bifluoride, tetrapropylammonium bifluoride, tetrabutylammonium bifluoride, tetrapentylammonium bifluoride, tetrahexyl Wherein the cleaning liquid composition comprises at least one selected from the group consisting of ammonium bifluoride, tetraheptylammonium bifluoride, and tetraoctylammonium bifluoride.
The cleaning liquid composition for removing photoresist according to claim 1, wherein the alkanesulfonic acid having 1 to 4 carbon atoms includes at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid and butanesulfonic acid.
The method of claim 1 wherein the azole-based compound is selected from the group consisting of 1,2-dimethylimidazole, 1-isopropylimidazole, 1-propyl-2-methylimidazole, benzylimidazole, , 3-triazole, benzotriazole, 5-amino-1-tetrazole, and 5-benzyl-1-tetrazole.
The cleaning liquid composition of claim 1, wherein the organic solvent is a polar protic solvent.
The composition according to claim 1, which comprises 1 to 20% by weight of at least one compound selected from the group consisting of compounds represented by formulas (1) and (2), 1 to 20% by weight of an alkanesulfonic acid having 1 to 4 carbon atoms, 0.1 to 5% And 60 to 97% of an organic solvent.
The cleaning liquid composition for removing photoresist according to claim 1, wherein the photoresist is modified during a dry etching process.
The cleaning liquid composition for removing photoresist according to claim 1, wherein the photoresist has a metal film formed thereunder.
11. The cleaning liquid composition according to claim 10, wherein the metal film is an aluminum-based metal film.
The cleaning liquid composition for removing photoresist according to claim 1, wherein the photoresist has a silicon oxide film formed thereunder.
I) forming a metal film on the substrate;
II) forming a silicon oxide film on the metal film;
III) forming a photoresist pattern on the silicon oxide film by a photolithography process;
(IV) dry etching the silicon oxide film on which the photoresist pattern is formed; And
V) cleaning the etched film with the cleaning composition according to claims 1 to 12;
And forming a semiconductor layer on the semiconductor substrate.